Structure–reactivity relationship for alcohol oxidations via hydride transfer to a carbocationic oxidizing agent

Second‐order rate constants were determined for the oxidation of 27 alcohols (R¹R²CHOH) by a carbocationic oxidizing agent, 9‐phenylxanthylium ion, in acetontrile at 60 °C. Alcohols include open‐chain alkyl, cycloalkyl, and unsaturated alcohols. Kinetic isotope effects for the reaction of 1‐phenylethanol were determined at three H/D positions of the alcohol (KIE_α‐D = 3.9, KIE_β‐D3 = 1.03, KIE_OD = 1.10). These KIE results are consistent with those we previously reported for the 2‐propanol reaction, suggesting that these reactions follow a hydride‐proton sequential transfer mechanism that involves a rate‐limiting formation of the α‐hydroxy carbocation intermediate. Structure–reactivity relationship for alcohol oxidations was deeply discussed on the basis of the observed structural effects on the formation of the carbocationic transition state (C^δ+? OH). Efficiencies of alcohol oxidations are largely dependent upon the alcohol structures. Steric hindrance effect and ring strain relief effect win over the electronic effect in determining the rates of the oxidations of open‐chain alkyl and cycloalkyl alcohols. Unhindered secondary alkyl alcohols would be selectively oxidized in the presence of primary and hindered secondary alkyl alcohols. Strained C₇? C₁₁ cycloalkyl alcohols react faster than cyclohexyl alcohol, whereas the strained C₅ and C₁₂ alcohols react slower. Aromatic alcohols would be efficiently and selectively oxidized in the presence of aliphatic alcohols of comparable steric requirements. This structure–reactivity relationship for alcohol oxidations via hydride‐transfer mechanism is hoped to provide a useful guidance for the selective oxidation of certain alcohol functional groups in organic synthesis. Copyright © 2011 John Wiley & Sons, Ltd.